Patented Dec. 4, 1928.

1,693,907
UNITED STATES PATENT OFFICE.
EMIL LttsCHER, OF BASEL, swiTZERLAND, ASSIGNOR TO THE COMPANY ELEKTRI
ZITATSWERK LONZA, OF GAMPEL AND BASEL, SWITZERLAND.
MANUEFACTURE OF CROTONALDEHYDE FROM ACETALDEHYDE AND ALDOL.
No Drawing. Application filed April 25, 1927, Serial No. 186,591, and in Switzerland May 4, 1926.
In the technical manufacture of croton When the distillation is conducted in a
aldehyde there was hitherto used aldol which continuous way, outputs of crotonaldehyde
in its turn was obtained by treating acetalde are obtained, which may be of 95 to 98 per
hyde with alkaline reacting substances. The
s output in this manufacture was not quite cent of the theoretical value. If the opera
what one could wish, as in the aldolizing. tion takes place in this manner, the isolation 60
operation as well as in the distillation greatly of the aldol in pure state is not necessary.
disturbing secondary reactions are produced. If the solution of the alkalihydroxide is
In the processes hitherto disclosed for the caused to run directly into great, quantities
0. preparation of aldol, reaction mixtures Were of water-free acetaldehyde a great heating
formed, which according to the nature of the of the mass takes place" at the beginning, 65
used condensating agents required a separa which should be conveniently moderated by
tion of the pure aldol from the solid Salts an outer cooling. If, however, the alkali so
lution is caused to run into a mixture of
or aqueous solutions, an operation which was acetaldehyde and aldol, the reaction tempera
53 somewhat expensive owing to the great vis ture can easily be maintained for example at 70 .
cosity of the aldol and higher resin like con 30 to 40° C., provided that acetaldehyde is
densation products. If the crude aldol thus Euously added simultaneously with the
obtained is not purified, it is not adapted a.k.a. '
for the direct preparation of crotonaldehyde s The following example illustrates the im
for the reason that the salts which are pres proved process:
ent in solidor dissolved form have a disturb 100 kg. of acetaldehyde are mixed in an at 75
ing action on the distillation inasmuch as mosphere of nitrogen little by little with
they cause the formation of a resinous prod 200 cm, of a 5 per cent solution of sodium
uet, thus diminishing considerably the output
25 by losses which may attain 15 to 20 per cent lowed to risewhereby
hydroxide, the temperature is al
and more. slowly to about 30 to 35° C. 80
Now, it has been found that in the manu action mixture is still leftof for
After the addition of all the alkali, the re
some time at
facture of crotonaldehyde from acetalde this temperature. To the reaction mixture
hyde and aldol these drawbacks can be avoid there is then added 1 kg. of phosphoric
ed if acetaldehyde is combined in an atmos and a fractional distillation is performedacid
phere of nitrogen with only such a quantity a circulating atmosphere of nitrogen. in -85
of a diluted aqueous solution of a caustic Where operating in this manner, croton
alkali that subsequent neutralization of the aldehyde is obtained in a good output.
product of reaction by a mineral acid does not
cause precipitation, and if after addition of ofThe operation is effected in an atmosphere
nitrogen for the reason that acetaldehyde, 90
a mineral acid the reaction mixture contain
ing aldol, acetaldehyde and a little salt is for example when being stirred, very easily
fractionally distilled without previous puri mation ofoxygen
absorbs
acetic
which gives rise to the for
acid, whereby the condensa
fication or separation, within a circulating tion would be unfavorably affected.
40 atmosphere of nitrogen. In the manufacture of aldol from acetal 95
The quantity of alkalihydroxide, which is dehyde there was hitherto employed alkaline
used in the present case, is only about 1 to 2 condensing
hundredth per cent of the weight of acetalde more. The agents use of
in quantities of 0,5% and
such considerable quanti
hyde when in form of a diluted watery solu ties of alkalis causes, however, on the neu
45s tion. Thess advantages of such a weak alkali
concentration consist in that first an extreme separation of salts which by
tralization of the alkali
on
a mineral acid a 0.
the further treat
ly pure aldol, that is one which contains only . ment of the aldol have an interfering or resi
traces of higher condensation products is nating action. . ,
formed, that secondly no precipitation is Instead of phosphoric acid sulfuric acid or
produced on the neutralization with a min any other convenient mineral acid can be 105.
eral acid, such as for example sulfuric acid used.
orphosphoric acid, and that thirdly this weak
salt concentration does not affect unfavorably What A
I claim is:
process for the manufacture of croton
the distillation or the transformation of the aldehyde from acetaldehyde and aldol, con
55 aldol to crotonaldehyde.
sisting in combining acetaldehyde in an at ll.0
 2 1,693,907
mosphere of nitrogen with only such a quan- tilling fractionally this reaction mixture
tity of a diluted aqueous solution of a caus- without previous purification or separation
tic alkali as to not cause any precipitation on within a circulating atmosphere of nitrogen. 10
subsequent neutralization, then adding a In witness whereof I have hereunto signed
5 mineral acid to the reaction product to ob- my name this 14th day of April, 1927.
tain a reaction
acetaldehyde and mixture containing
a little salt, and finallyaldol,
dis. EMILLUSCHER.